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Lithium-ion batteries are the most ubiquitous energy storage devices in our everyday lives. However, their energy storage capacity fades over time due to chemical and structural changes in their components, via different degradation mechanisms. Understanding and mitigating these degradation mechanisms is key to reducing capacity fade, thereby enabling improvement in the performance and lifetime of Li-ion batteries, supporting the energy transition to renewables and electrification. In this endeavor, surface analysis techniques are commonly employed to characterize the chemistry and structure at reactive interfaces, where most changes are observed as batteries age. However, battery electrodes are complex systems containing unstable compounds, with large heterogeneities in material properties. Moreover, different degradation mechanisms can affect multiple material properties and occur simultaneously, meaning that a range of complementary techniques must be utilized to obtain a complete picture of electrode degradation. The combination of these issues and the lack of standard measurement protocols and guidelines for data interpretation can lead to a lack of trust in data. Herein, we discuss measurement challenges that affect several key surface analysis techniques being used for Li-ion battery degradation studies: focused ion beam scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and time-of-flight secondary ion mass spectrometry. We provide recommendations for each technique to improve reproducibility and reduce uncertainty in the analysis of NMC/graphite Li-ion battery electrodes. We also highlight some key measurement issues that should be addressed in future investigations.

Core–shell nanoparticles have attracted much attention in recent years due to their unique properties and their increasing importance in many technological and consumer products. However, the chemistry of nanoparticles is still rarely investigated in comparison to their size and morphology. In this review, the possibilities, limits, and challenges of X-ray photoelectron spectroscopy (XPS) for obtaining more insights into the composition, thickness, and homogeneity of nanoparticle coatings are discussed with four examples: CdSe/CdS quantum dots with a thick coating and a small core; NaYF4-based upconverting nanoparticles with a large Yb-doped core and a thin Er-doped coating; and two types of polymer nanoparticles with a poly(tetrafluoroethylene) core with either a poly(methyl methacrylate) or polystyrene coating. Different approaches for calculating the thickness of the coating are presented, like a simple numerical modelling or a more complex simulation of the photoelectron peaks. Additionally, modelling of the XPS background for the investigation of coating is discussed. Furthermore, the new possibilities to measure with varying excitation energies or with hard-energy X-ray sources (hard-energy X-ray photoelectron spectroscopy) are described. A discussion about the sources of uncertainty for the determination of the thickness of the coating completes this review.

A method for the rapid determination of theoretical relative sensitivity factors (RSFs) for hard X-ray photoelectron spectroscopy (HAXPES) instruments of any type and photon energy has been developed. We develop empirical functions to describe discrete theoretically calculated values for photoemission cross-sections and asymmetry parameters across the photon energy range from 1.5 keV - 10 keV for all elements from lithium to californium. The formulae describing these parameters, in conjunction with similar practical estimates for inelastic mean free paths, allow the calculation of a full set of theoretical sensitivity factors for a given X-ray photon energy, X-ray polarisation and instrument geometry. We show that the anticipated errors on these RSFs are less than the typical errors generated by extracting X-ray photoelectron spectroscopy (XPS) intensities from the spectra, and thus enable adequate quantification for any XPS/HAXPES experiment up to 10 keV. A spreadsheet implementation of this method is provided in the supporting information, along with example RSFs for existing commercial instruments.

Quantification of the composition of binary mixtures in secondary ion mass spectrometry (SIMS) is required in the analyses of technological materials from organic electronics to drug delivery systems. In some instances, it is found that there is a linear dependence between the composition, expressed as a ratio of component volumes, and the secondary ion intensities, expressed as a ratio of intensities of ions from each component. However, this ideal relationship fails in the presence of matrix effects and linearity is observed only over small compositional ranges, particularly in the dilute limits. In this paper, we assess an empirical method, which introduces a power law dependence between the intensity ratio and the volume fraction ratio. A previously published physical model of the organic matrix effect is employed to test the limits of the method and a mixed system of 3,3′-bis(9-carbazolyl) biphenyl and tris(2-phenylpyridinato)iridium (III) is used to demonstrate the method. This paper introduces a two-point calibration, which determines both the exponent in the power law and the sensitivity factor for the conversion of ion intensity ratio into volume fraction ratio. We demonstrate that this provides significantly improved accuracy, compared with a one-point calibration, over a wide compositional range in SIMS quantification and with a weak dependence on matrix effects. Because the method enables the use of clearly identifiable secondary ions for quantitative purposes and mitigates commonly observed matrix effects in organic materials, the two-point calibration method could be of significant benefit to SIMS analysts.

We introduce a technique for the directed transfer of molecules from an adjacent reservoir onto a sample surface inside the vacuum chamber of a ToF-SIMS instrument using gas cluster ion beam (GCIB) sputtering. An example application for in situ matrix-enhanced secondary ion mass spectrometry (ME SIMS) is provided. This protocol has attractive features since most modern SIMS instruments are equipped with a GCIB gun. No solvents are required that would delocalize analytes at the surface, and the transfer of matrix molecules can be interlaced with SIMS depth profiling and 3D imaging sputtering and analysis cycles, which is not possible with conventional ME SIMS strategies. The amount of molecular deposition can be finely tuned, which is important for such a surface sensitive technique as SIMS. To demonstrate the concept, we used 2,5-DHB as a matrix for the enhancement of three drug molecules embedded in a tissue homogenate. By automatic operation of sputter deposition and erosion (cleanup) cycles, depth profiling could be achieved with ME SIMS with good repeatability (

Peptide-coated surfaces are widely employed in biomaterial design, but quantifiable correlation between surface composition and biological response is challenging due to, for example, instrumental limitations, a lack of suitable model surfaces or limitations in quantitatively correlating data from different surface analytical techniques. Here, we first establish a reference material that allows control over amino acid content. Reversible addition-fragmentation chain-transfer (RAFT) polymerisation is used to prepare a copolymer containing alkyne and furan units with well-defined chain length and composition. Huisgen Cu(I)-catalysed azide-alkyne cycloaddition reaction is used to attach the model azido-polyethyleneglycol-amide-modified pentafluoro-l-phenylalanine to the polymer. Different compositional ratios of the polymer provide a surface with varying amino acid content that is analysed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Nitrogen-related signals are compared with fluorine signals from both techniques. Fluorine and nitrogen signals from both techniques are found to be related to the copolymer compositions, but the homopolymer data deviate from this trend. The approach is then translated to a heparin-binding peptide that supports cell adhesion. Human embryonic stem cells cultured on copolymer surfaces presenting different amounts of heparin-binding peptide show strong cell growth while maintaining pluripotency after 72 h of culture. The early cell adhesion at 24 h can be correlated to the logarithm of the normalised CH4N+ ion intensity from ToF-SIMS data, which is established as a suitable and generalisable marker ion for amino acids and peptides. This work contributes to the ability to use ToF-SIMS in a more quantitative manner for the analysis of amino acid and peptide surfaces.

Modern mass spectrometry techniques produce a wealth of spectral data, and although this is an advantage in terms of the richness of the information available, the volume and complexity of data can prevent a thorough interpretation to reach useful conclusions. Application of molecular formula prediction (MFP) to produce annotated lists of ions that have been filtered by their elemental composition and considering structural double bond equivalence are widely used on high resolving power mass spectrometry datasets. However, this has not been applied to secondary ion mass spectrometry data. Here, we apply this data interpretation approach to 3D OrbiSIMS datasets, testing it for a series of increasingly complex samples. In an organic on inorganic sample, we successfully annotated the organic contaminant overlayer separately from the substrate. In a more challenging purely organic human serum sample we filtered out both proteins and lipids based on elemental compositions, 226 different lipids were identified and validated using existing databases, and we assigned amino acid sequences of abundant serum proteins including albumin, fibronectin, and transferrin. Finally, we tested the approach on depth profile data from layered carbonaceous engine deposits and annotated previously unidentified lubricating oil species. Application of an unsupervised machine learning method on filtered ions after performing MFP from this sample uniquely separated depth profiles of species, which were not observed when performing the method on the entire dataset. Overall, the chemical filtering approach using MFP has great potential in enabling full interpretation of complex 3D OrbiSIMS datasets from a plethora of material types.

The advancement of analytical methods for nanoparticle measurements is critical both for the growing industrial exploitation of engineered nanoparticles and for developing robust strategies to understand and control the concentration of nanomaterials in humans and the environment. For high value nanoparticles, the measurement of nanoparticle number concentration in a liquid directly impacts the ability to assess the scale and reproducibility of the production process, it allows optimisation of efficiency and supports regulatory compliance. This measurement is also useful to monitor and control the intentional or accidental release of engineered nanoparticles into the environment at the production plant, as well as by end-users., peer-reviewed

This glossary provides a formal vocabulary of terms for concepts in surface analysis and gives clear definitions to those who utilize surface chemical analysis or need to interpret surface chemical analysis results but are not themselves surface chemists or surface spectroscopists.

The ability to measure the internal chemical distribution of particles is of significant benefit to the development and testing of products relevant to the pharmaceutical, agrichemical, and food in...

Accurate and reproducible measurement of the structure and properties of high-value nanoparticles is extremely important for their commercialization. A significant proportion of engineered nanopart...

Main text The key comparison CCQM-K157 for the thickness measurement of HfO2 films was performed by the Surface Analysis Working Group (SAWG) of the Consultative Committee for Amount of Substance (CCQM). The aim of CCQM-K157 is to establish the measurement traceability and to ensure the equivalency in the measurement capability of national metrology institutes for the thickness measurement of HfO2 films. In this key comparison, the thicknesses of six HfO2 films with the nominal thickness range from 0.7 nm to 6 nm were compared by x-ray photoelectron spectroscopy (XPS), x-ray reflectometry (XRR), transmission electron microscopy (TEM), spectroscopic ellipsometry (SE) and medium energy ion scattering spectrometry (MEIS). To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Transition-edge sensors (TESs) are capable of highly accurate single particle energy measurement. TESs have been used for a wide range of photon detection applications, particularly in astronomy, but very little consideration has been given to their capabilities as electron calorimeters. Existing electron spectrometers require electron filtering optics to achieve energy discrimination, but this step discards the vast majority of electrons entering the instrument. TESs require no such energy filtering, meaning they could provide orders of magnitude improvement in measurement rate. To investigate the capabilities of TESs in electron spectroscopy, a simulation pipeline has been devised. The pipeline allows the results of a simulated experiment to be compared with the actual spectrum of the incident beam, thereby allowing measurement accuracy and efficiency to be studied. Using Fisher information, the energy resolution of the simulated detectors was also calculated, allowing the intrinsic limitations of the detector to be separated from the specific data analysis method used. The simulation platform has been used to compare the performance of TESs with existing X-ray photoelectron spectroscopy (XPS) analysers. TESs cannot match the energy resolution of XPS analysers for high-precision measurements but have comparable or better resolutions for high count rate applications. The measurement rate of a typical XPS analyser can be matched by an array of 10 TESs with 120 microsecond response times and there is significant scope for improvement, without compromising energy resolution, by increasing array size., Comment: 9 pages, 3 figures

This paper provides a description of the transmission function of an XPS instrument operating with exchangeable Al Kα (1486.6 eV) and Ag Lα (2984.3 eV) sources. Both sources use the same quartz crystal monochromator and illuminate the same area of the sample. The transmission-function-corrected data from sputter cleaned gold provides a useful reference material to calibrate other instruments of the same type. Sensitivity factors for Ag Lα and Al Kα are calculated from photoionisation cross sections and electron effective attenuation lengths. These compare well to previous experimental values and data acquired from ionic liquids. The intensity of the Ag Lα source is found to be approximately 50 times lower than the Al Kα source. This, coupled with generally lower photoemission efficiencies, results in noisier data or extended acquisition times. However, there are clear advantages to using the Ag Lα source to analyse certain elements where additional core levels can be accessed and for many technologically important elements where interference from Auger electron peaks can be eliminated. The combination of calibrated data from both sources provides direct and easily interpreted insight into the depth distribution of chemical species. This could be particularly important for topographic samples, where angle resolved experiments are not always helpful. We also demonstrate, using thin coatings of chromium and carbon, that the inelastic background in Ag Lα wide-scan spectra has a significantly increased information depth compared to Al Kα.

We describe a method for the intensity calibration of XPS instruments using polyethylene as the reference material. Previous methods for have employed noble metals, such as gold, silver and copper. Polyethylene has a number of advantages over these. It has far fewer photoelectron and Auger electron peaks than such metals, i.e. the spectrum largely comprises inelastic background over a wide and continuous range of kinetic energies. The XPS spectrum can be described by a mathematical function enabling simple and noise-free implementation of the reference spectrum. Polyethylene can be cleaned ex-situ using a sharp knife or razor blade to remove trace oxygen and, due to its chemical composition, should not be affected by adventitious carbon contamination. Thus, an ion source for sputter cleaning is not required, although an electron flood source for charge compensation is required. The drawback to using polyethylene is that the photoelectron yield is far lower than gold or silver and this necessitates longer acquisition times and removal of dark noise. Longer acquisition times carry the risk of damaging the polyethylene surface and we show that, even if damage does occur, it has negligible effect on the XPS background intensity. The reference spectrum is valid for monochromated Al Kα XPS instruments with a monochromator-sample-analyser angle close to 60°.

Quantum circuits show unprecedented sensitivity to external fluctuations compared to their classical counterparts, and it can take as little as a single atomic defect somewhere in a mm-sized area to completely spoil device performance. For improved device coherence it is thus essential to find ways to reduce the number of defects, thereby lowering the hardware threshold for achieving fault-tolerant large-scale error-corrected quantum computing. Given the evasive nature of these defects, the materials science required to understand them is at present in uncharted territories, and new techniques must be developed to bridge existing capabilities from materials science with the needs identified by the superconducting quantum circuit community. In this paper, we give an overview of methods for characterising the chemical and structural properties of defects in materials relevant for superconducting quantum circuits. We cover recent developments from in-operation techniques, where quantum circuits are used as probes of the defects themselves, toin situanalysis techniques and well-establishedex situmaterials analysis techniques. The latter is now increasingly explored by the quantum circuits community to correlate specific material properties with qubit performance. We highlight specific techniques which, given further development, look especially promising and will contribute towards a future toolbox of material analysis techniques for quantum.

Hard X-ray Photoelectron Spectroscopy (HAXPES) provides minimally destructive depth profiling into the bulk, extending the photoelectron sampling depth. Detection of deeply buried layers beyond the elastic limit is enabled through inelastic background analysis. To test the robustness of this technique, we present results on a thin (18 nm) layer of metal–organic complex buried up to 200 nm beneath organic material. Overlayers with thicknesses 25–140 nm were measured using photon energies ranging 6–10 keV at the I09 end station at Diamond Light Source, and a new fixed energy Ga Kα (9.25 keV) laboratory-based HAXPES spectrometer was also used to measure samples with overlayers up to 200 nm thick. The sampling depth was varied: at Diamond Light Source by changing the photon energy, and in the lab system by performing angle-resolved measurements. For all the different overlayers and sampling depths, inelastic background modelling consistently provided thicknesses which agreed, within reasonable error, with the ellipsometric thickness. Relative sensitivity factors were calculated, and these factors consistently provided reasonable agreement with the expected nominal stoichiometry, suggesting the calculation method can be extended to any element. These results demonstrate the potential for the characterisation of deeply buried layers using synchrotron and laboratory-based HAXPES.

We introduce a technique for the directed transfer of molecules from an adjacent reservoir onto a sample surface inside the vacuum chamber of a ToF-SIMS instrument using gas cluster ion beam (GCIB) sputtering. An example application for

Label-free protein characterization at surfaces is commonly achieved using digestion and/or matrix application prior to mass spectrometry. We report the assignment of undigested proteins at surfaces in situ using secondary ion mass spectrometry (SIMS). Ballistic fragmentation of proteins induced by a gas cluster ion beam (GCIB) leads to peptide cleavage producing fragments for subsequent OrbitrapTM analysis. In this work we annotate 16 example proteins (up to 272 kDa) by de novo peptide sequencing and illustrate the advantages of this approach by characterizing a protein monolayer biochip and the depth distribution of proteins in human skin., Label-free protein characterization at surfaces requires digestion or matrix application prior to mass spectrometry. Here, the authors report the assignment of undigested proteins at surfaces by de novo sequencing and apply the methodology to a protein monolayer biochip and for in situ depth profiling of proteins through human skin.

X-ray photoelectron spectroscopy is a highly surface-sensitive analytical technique, capable of providing quantitative information on the chemical composition of materials within the top ∼10 nm of their surface. For samples consisting of distinct underlayer and overlayer materials, the thickness of the coating can also be determined if it falls within this ∼10 nm information depth, which is often the case for peptide layers. Such measurements are simple to perform for flat samples and can also be performed on nanoparticulate samples provided that either the core radius or total particle radius are known. Here, we describe a straightforward protocol for obtaining such measurements from peptide coatings on both flat surfaces and nanoparticles, including preparation of nanoparticle samples from suspension, data acquisition, and analysis.

X-ray photoelectron spectroscopy is a highly surface-sensitive analytical technique, capable of providing quantitative information on the chemical composition of materials within the top ∼10 nm of their surface. For samples consisting of distinct underlayer and overlayer materials, the thickness of the coating can also be determined if it falls within this ∼10 nm information depth, which is often the case for peptide layers. Such measurements are simple to perform for flat samples and can also be performed on nanoparticulate samples provided that either the core radius or total particle radius are known. Here, we describe a straightforward protocol for obtaining such measurements from peptide coatings on both flat surfaces and nanoparticles, including preparation of nanoparticle samples from suspension, data acquisition, and analysis.

Characterization of Nanoparticles: Measurement Processes for Nanoparticles surveys this fast growing field, including established methods for the physical and chemical characterization of nanoparticles. The book focuses on sample preparation issues (including potential pitfalls), with measurement procedures described in detail. In addition, the book explores data reduction, including the quantitative evaluation of the final result and its uncertainty of measurement. The results of published inter-laboratory comparisons are referred to, along with the availability of reference materials necessary for instrument calibration and method validation. The application of these methods are illustrated with practical examples on what is routine and what remains a challenge. In addition, this book summarizes promising methods still under development and analyzes the need for complementary methods to enhance the quality of nanoparticle characterization with solutions already in operation.

This chapter provides an overview of the use of optical absorption spectroscopy for the measurement of nanoparticles. Virtually, all nanoparticles scatter and absorb light to the extent that, in sufficient concentration, they can be detected using a traditional ultraviolet–visible spectrophotometer. The technique is useful to determine the concentration of particles, provided that either a reference material is available or that the material is very well understood. In general, it is not possible to simultaneously determine the concentration, size, or refractive index of particles using UV–vis spectrophotometry on its own. However, in combination with other methods, it is a useful technique, especially as a quality control method. In the case of metal particles, there can be plasmonic features in the UV–vis spectrum that are sensitive to local refractive index, particle size, shape, and agglomeration. The sensitivity to each of these parameters is exquisite; however, it is not recommended to use UV–vis spectrophotometry independently to measure these parameters because of the associated uncertainties. Gold is the most extensively studied of these plasmonic metals, and the relevant literature for gold nanoparticles is reviewed.

The use of X-ray photoelectron spectroscopy (XPS) for the analysis of nanoparticles is described. The method has been extensively used to identify elements, their chemical state, and their concentration at surfaces for many years. It is the most accurate method for measuring the composition and thickness of thin (

Matrix effects in the secondary ion mass spectrometry (SIMS) of selected elemental systems have been analyzed to investigate the applicability of a mathematical description of the matrix effect, called here the charge transfer (CT) model. This model was originally derived for proton exchange and organic positive secondary ions, to characterise the enhancement or suppression of intensities in organic binary systems. In the systems considered in this paper protons are specifically excluded, which enables an assessment of whether the model applies for electrons as well. The present importance is in organic systems but, here we analyse simpler inorganic systems. Matrix effects in elemental systems cannot involve proton transfer if there are no protons present but may be caused by electron transfer and so electron transfer may also be involved in the matrix effects for organic systems. There are general similarities in both the magnitudes of the ion intensities as well as the matrix effects for both positive and negative secondary ions in both systems and so the CT model may be more widely applicable. Published SIMS analyses of binary elemental mixtures are analyzed. The data of Kim et al., for the Pt/Co system, provide, with good precision, data for such a system. This gives evidence for the applicability of the CT model, where electron, rather than proton, transfer is the matrix enhancing and suppressing mechanism. The published data of Prudon et al., for the important Si/Ge system, provides further evidence for the effects for both positive and negative secondary ions and allows rudimentary rules to be developed for the enhancing and suppressing species.

The factors that affect the accuracy and precision of differential centrifugal sedimentation (DCS) for the analysis of nanoparticle concentration are described. Particles are separated by their sedimentation rate and detected using light absorption. In principle, the relative concentration of particles in different populations can be found, but the uncertainty in such measurements is unclear. We show that the most appropriate measurement of particle concentration using this technique is the mass concentration, rather than the number concentration. The relative mass concentration of two discrete populations can be measured with reasonable precision, usually without resorting to complicated data analysis. We provide practical approaches to find the relative mass concentrations for two cases: spherical particles of different materials and agglomerated particles of the same material. For spherical particles made of different materials, naive analysis of the results can provide relative mass concentrations that are many orders of magnitude in error. Correction factors can be calculated that reduce the error to less than 50%. In the case of agglomerated particles we show that errors of less than 20% are possible and demonstrate, in the case of gold particles, that a combination of UV-visible spectroscopy and DCS enable practical values of mass and number based particle concentrations to be obtained.

The successful translation of nanoparticle-based systems into commercial products depends upon the ability to reliably measure important physical and chemical properties of these particles. The density of nanoparticles is one such property, because it provides important information about the composition of the material. In this work, an analytical centrifugation approach based on line-start centrifugal sedimentation and flotation measurements is described. The two independent measurements permit both the size and the density of these nanoparticles to be determined with excellent precision. A set of monodisperse polystyrene nanoparticles of different sizes is used to demonstrate this method. The density and size measurements are validated by comparison to accurate Small Angle X-ray Scattering (SAXS) analysis for particles within the size range of SAXS, i.e. less than ∼300 nm in diameter. Both sedimentation and flotation measurements produce consistent high resolution size distributions of the particles and the measured size and density values are identical, within experimental uncertainty, to the SAXS results. This approach has the potential to provide useful characterisation of a range of particles of interest, for example, for medical application, such as liposomes and polymeric drug carriers.

The International Standard ISO 22415 provides methods to measure sputtering yield volumes of organic test materials using argon cluster ions. The test materials should consist of thin films of known thicknesses between 50 nm and 1 000 nm. The format of the test materials, the measurement of sputtering ion dose, sputtered depth and reporting requirements for sputtering yield volumes are described.

In this work, we explore the possibility of finding a simple mathematical function that describes XPS background intensities as a function of energy and depth of emission. We describe the shape of the global structure of the background in XPS survey spectra for organic overlayer films with thicknesses greater than ~10 nm. In this situation, the shape of XPS backgrounds becomes statistical, and the detailed structure of, for example, energy-loss functions and elastic-scattering cross sections can be disregarded. Using Irganox 1010 as a model organic overlayer on silicon dioxide, gold, and silver substrates, a consistent description of the XPS background can be found, and overlayer thicknesses greater than 50 nm can be measured in the case of gold substrates. Furthermore, by using a suitable subset of these spectra, it is possible to separate the influence of overlayer thickness, electron kinetic energy, and intensity on the global shape of the spectrum. We show that it is possible to fully describe the shape of calibrated XPS survey spectra with reasonable accuracy for samples that have organic overlayers using only binding energy and sensitivity factor data. The same functions are shown to provide a reasonable description of the XPS spectra of silicon with an oxide overlayer.

X-ray photoelectron spectroscopy (XPS) was used in conjunction with gas cluster ion source etching to analyze polystyrene and polyvinylpyrrolidone multilayer samples, total thickness ~15 μm, to establish optimal conditions for depth profiles over many μm in depth. Using standard conditions, these samples demonstrate a reduction in depth resolution and sputtering yield, which is shown to be partly due to X-ray–induced damage and partly due to roughening of the sputtered surface. By limiting the X-ray exposure, it was possible to retain depth resolution to a depth of approximately 5 μm; to obtain useful depth profiles beyond this depth, it was necessary to use sample rotation. The use of optimized conditions allowed the chemical integrity of the polymer layers to remain intact during the etching process with relatively sharp interfaces over the full depth of the films. Both the elemental intensities in XPS and the line shape of the C 1s peak could be used to determine the differences in chemical structure of the films in the depth profile. Detailed analysis suggests that a “stepwise” rotation scheme can maintain depth resolution better than continuous rotation during sputtering.

Protein characterisation at surfaces currently requires digestion prior to either liquid extraction of the protein for mass spectrometry analysis or in situ matrix-assisted desorption/ionisation. Here, we show that direct assignment of individual proteins and mixtures at surfaces can be achieved by employing secondary ion mass spectrometry (SIMS) with gas cluster ion beam (GCIB) bombardment and an Orbitrap™ analyser. Potential applications of the method are illustrated by demonstrating imaging of a protein film masked by a gold grid and the analysis of a protein monolayer biochip.

Over the past three decades, the widespread utility and applicability of X-ray photoelectron spectroscopy (XPS) in research and applications has made it the most popular and widely used method of surface analysis. Associated with this increased use has been an increase in the number of new or inexperienced users which has led to erroneous uses and misapplications of the method. This article is the first in a series of guides assembled by a committee of experienced XPS practitioners that are intended to assist inexperienced users by providing information about good practices in the use of XPS. This first guide outlines steps appropriate for determining whether XPS is capable of obtaining the desired information, identifies issues relevant to planning, conducting and reporting an XPS measurement, and identifies sources of practical information for conducting XPS measurements. Many of the topics and questions addressed in this article also apply to other surface-analysis techniques.

The industrial exploitation of high value nanoparticles is in need of robust measurement methods to increase the control over product manufacturing and to implement quality assurance. InNanoPart, a European metrology project responded to these needs by developing methods for the measurement of particle size, concentration, agglomeration, surface chemistry and shell thickness. This paper illustrates the advancements this project produced for the traceable measurement of nanoparticle number concentration in liquids through small angle X-ray scattering (SAXS) and single particle inductively coupled plasma mass spectrometry (spICPMS). It also details the validation of a range of laboratory methods, including particle tracking analysis (PTA), dynamic light scattering (DLS), differential centrifugal sedimentation (DCS), ultraviolet visible spectroscopy (UV-vis) and electrospray-differential mobility analysis with a condensation particle counter (ES-DMA-CPC). We used a set of spherical gold nanoparticles with nominal diameters between 10 nm and 100 nm and discuss the results from the various techniques along with the associated uncertainty budgets.

The industrial exploitation of high value nanoparticles is in need of robust measurement methods to increase the control over product manufacturing and to implement quality assurance. InNanoPart, a European metrology project responded to these needs by developing methods for the measurement of particle size, concentration, agglomeration, surface chemistry and shell thickness. This paper illustrates the advancements this project produced for the traceable measurement of nanoparticle number concentration in liquids through small angle X-ray scattering (SAXS) and single particle inductively coupled plasma mass spectrometry (spICPMS). It also details the validation of a range of laboratory methods, including particle tracking analysis (PTA), dynamic light scattering (DLS), differential centrifugal sedimentation (DCS), ultraviolet visible spectroscopy (UV-vis) and electrospray-differential mobility analysis with a condensation particle counter (ES-DMA-CPC). We used a set of spherical gold nanoparticles with nominal diameters between 10 nm and 100 nm and discuss the results from the various techniques along with the associated uncertainty budgets.

Measuring the number concentration of colloidal nanoparticles (NPs) is critical for assessing reproducibility, enabling compliance with regulation, and performing risk assessments of NP-enabled products. For nanomedicines, their number concentration directly relates to their dose. However, the lack of relevant reference materials and established traceable measurement approaches make the validation of methods for NP number concentration difficult. Furthermore, commercial products often exhibit agglomeration, but guidelines for dealing with nonideal samples are scarce. We have compared the performance of five benchtop measurement methods for the measurement of colloidal number concentration in the presence of different levels of agglomeration. The methods are UV-visible spectroscopy, differential centrifugal sedimentation, dynamic light scattering, particle tracking analysis, and single-particle inductively coupled plasma mass spectrometry. We find that both ensemble and particle-by-particle methods are in close agreement for monodisperse NP samples and three methods are within 20% agreement for agglomerated samples. We discuss the sources of measurement uncertainties, including how particle agglomeration affects measurement results. This work is a first step toward validation and expansion of the toolbox of methods available for the measurement of real-world NP products.